Composition of matter with low cholesterol content and containing wool grease alcohols as major component and method

ABSTRACT

A new and useful dispersing and emulsifying agent derived from wool grease made by separating cholesterol from the unsaponifiables and replacing the cholesterol with Beta sitosterol, to form an improved essentially wool wax alcohol product.

United States Patent [191 Julian [451 Jan. 16, 1973 [76] Inventor: Percy L. Julian, 515 North East Avenue, Oak Park, 111. 60302 221 Filed: April23, 1971 211 Appl.No.: 137,028

[52] US. Cl ..424/358 [51] Int. Cl. ..A6lk 7/00, A611 9/06 [58] Field of Search ..424/358 [56] References Cited UNITED STATES PATENTS 3272.851 9/1966 Sunde et a1 ..260/428 3,101 ,300 8/1963 Siegal et a1. ..424/358 2.900.307 8/1959 Wei ..424/358 1,725,334 11/1955 Conrad et a1 ..424/358 2,676,149 4/1954 Woods et a1 ..252/42.1

OTHER PUBLlCATlONS Cockbain et a1. Trans. Faraday Soc. 47; 322-330 1951) Adsorbed Films at Oil-Water lnterfaces Karabinos et al. J. Am. Oil Chemists Soc. 31; 136 (1954) Synthesis and Comparative Detergency of Built Polyethenoxy Sitosterols Feldman et a1. Biochem. Biophys. Acta 125(1); 136-147 1966) Phase Distribution of Sterols Primary ExaminerShep K. Rose Att0rney-Dawson, Tilton, Fallon & Lungm us [57] ABSTRACT A new and useful dispersing and emulsifying agent derived from wool grease made by separating cholesterol from the unsaponifiables and replacing the cholesterol with Bsitosterol', to form an improved essentially wool wax alcohol product.

8 Claims, No Drawings COMPOSITION OF MATTER WITH LOW CHOLESTEROL CONTENT AND CONTAINING WOOL GREASE ALCOHOLS AS MAJOR COMPONENT AND METHOD BACKGROUND OF INVENTION One of the earliest attacks on environmental pollution resided in the program of what to do in England with the grease that had to be scoured, sometimes with detergents, from native wool, prior to its use. That was in the height of the wool industry. The British government was compelled to crack down upon the dumping of this grease into the sewers and streams, resulting in clogging the former and converting the latter into veritable cess pools. As is very often the case, the remedy came in a new invention, resulting in the birth of what is now known as Lanolin, a wool grease freed from dirt; deodorized and sometimes bleached. As is well known, Lanolin has become a sine qua non for the cosmetic industry, primarily because of its capacity to absorb water with the formation of emulsions with light minerals oils, and heavy petrolatum, such as Vaseline, etc.

The success of Lanolin led to a more refined and for many purposes more effective product, namely, Wool Wax Alcohols, whose emulsifying characteristics far exceed those of Lanolin itself. Indeed, these alcohols when dissolved in eight to times their weight of certain mineral oils cause the solution to absorb more than 250 times their (the alcohols) weight of water, resulting in beautiful and quite stable creams. Thus, these wool wax alcohols have enhanced, in large part, the variety of face creams, cleansing creams, hair creams and the like, available in the toiletries of feminine and, indeed, masculine make-up." Wool wax alcohols are, therefore, today an important article of commerce.

Wool wax is composed, for the most part, of esters, compounds of alcohols with a variety of fatty acids. Prominent among these alcohols is another useful product, cholesterol, which constitutes as high as 25 to 32 percent of the alcohol fraction of wool grease. Alongside cholesterol, there are other alcohols, such as lanosterol, and lower molecular weight alcohols, some of which are glycols. The alcohol fraction is separated by saponification of the wool grease, and separation of the alcohols from the saponification mixture of free fatty acids and wool wax alcohols.

From the alcohol portion, over the past two and a half decades, cholesterol has been separated commercially. Prior to this event, commercial cholesterol was available largely from brains and spinal cords. The rise of labor costs in the separation of spinal cords; the growth of the pet animal feeds (where brains and other offals found exploitation); and the supplanting of cholesterol (for sex and adrenal hormone manufacturing) by such naturally-occurring sterols and steroids as stigmasterol (from soybean oil), diosgenin (from the wild yams of the Dioscorea family), and hecogenin (from sisal juice) have resulted in the use of wool wax alcohols as the most economical source of cholesterol.

Cholesterol, however, has one use for which no other product has been able to supplant it, namely, the synthesis of Vitamin D a vitamin absolutely essential to the life and well-being of all two-footed animals.

With the growth of fowl as a major item in the human diet, the economical manufacture of cholesterol is, therefore, of definite industrial significance. Just in the last 25 years, the usage of synthetic Vitamin D in the United States alone, has risen from less than ten trillion International units annually to an estimated 650 trillion International units annually.

Moreover, the growing interest in the exploitation of liquid crystals, of which a large number are esters of cholesterol, is destined soon to find cholesterol in short supply. Significant is the fact that no other sterol esters have been found to exhibit the liquid crystal effects of most of the liquid crystal cholesterol esters. Another factor which may contribute to the shortage of cholesterol is the constantly growing replacement of wool by synthetic fibers. With wool scouring at an alltime low and the shutdown of many woolen mills, a more economic production of cholesterol must be achieved.

It has been demonstrated that cholesterol is in large part responsible for the unique ability of wool wax alcohols to form the remarkable water-in-oil emulsions, represented by the creams described above. It has also been demonstrated that the residual wool wax alcohols after removal of cholesterol are poor emulsifiers and virtually useless for the cosmetic creams and lotions described. Indeed, E. V. Truter (Cleaver-Hume Press, Ltd., London, 1956, p. in speaking of the extraction of cholesterol from wool grease, states: In recent years the growing demand for cholesterol has resulted in the adaptation of suitable old methods, and the development of new ones designed specifically for the extraction of cholesterol (from wool wax alcohols), the residual alcohols being of relatively little importanceexcept to the academic research worker.

Herein lies a great stumbling block to the use of wool wax alcohols (constituting almost 50 percent by weight of the wool grease) for the preparation of cholesterol, as is obvious from the following figures:

50 pounds Refined (molecularly distilled) wax alcohols are marketed at an average price of $1.50 per pound, or $75.00.

12 pounds pure U.S.P. cholesterol (the average quantity successfully extracted and refined from these 50 pounds) at ca. $6.00 per pound or $72.00.

Thus, why go to the trouble of preparing cholesterol from these valuable alcohols, since the residual alcohols, left after cholesterol extraction, are virtually useless? If, however, another and cheaper sterol could be found, which could be incorporated into the spent alcohols (the alcohols after removal of cholesterol) in such a manner and quantity as to bring these spent alcohols up to the emulsifying capacity of the cholesterol-bearing" wool wax alcohols, the economics of cholesterol extraction from wool grease would be greatly improved.

SUMMARY OF lNVENTlON It is, therefore, an object of the present invention to find a use for W001 wax alcohols after removal of the cholesterol therefrom.

It is a further object of the invention to devise, develop or locate a substance or substances which might replace cholesterol in wool wax alcohols, and

still bring about a wool wax alcohol mixture with emulsifying and other characteristics equal to or improved over intact wool wax alcohols.

Still another object of this invention is to replace the cholesterol in wool grease by another sterol, equal in stability and contributing essentially the same emulsifying, emollient and other significant properties to the wool wax alcohols as does cholesterol.

Still a further object of the invention bearing in mind the important emollient characteristics of wool wax alcohol creams, and possible absorption of certain ingredients into the blood stream, thus possibly upsetting dangerously the maximum cholesterol allowance in the blood stream is to replace cholesterol in wool wax alcohols with another sterol which is nonirritating, non-toxic and non-controversial from a health point of view, yet retaining essentially the same emulsifying, emollient and other desirable properties as unaltered natural wool wax alcohols.

Yet another object of the invention is to reduce mar kedly the amount of cholesterol present in wool wax alcohols.

Still another object of this invention is to replace cholesterol in wool wax alcohols, wholly or in part, with a sterol similar in structure, but much less expensive than cholesterol, yet extending to the wool wax alcohols essentially the same, or even enhanced, desirable characteristics as are em bodied in the intact" wool wax alcohols.

Yet a valuable object of this invention is to improve the economics of cholesterol manufacture, via extraction from wool wax alcohols, by almost doubling the present financial return from wool wax alcohols, and thus enhancing the prospects of cholesterol production on a scale to meet indispensible human and animal health needs and the presently growing demand.

Still a final object of this invention is to find satisfactory methods for incorporating into spent" wool wax alcohols (wool wax alcohols from which cholesterol has been extracted substantially wholly or in part) a sterol which enhances and/or equals the desirable characteristics hitherto attributed to cholesterol.

l have found that the objects of this invention have been achieved by replacing the cholesterol in wool wax alcohols by Sitosterol" from soybean oil, or from other sources such as Tallol, or sometimes called Tall Oil (from waste paper pulping liquors), cottonseed oil, etc. At the present time thousands of tons of such sitosterols are available at only a fraction of the cost of cholesterol. Moreover, I have found that the other sterols present in small quantities in the naturally-occurring sitosterols," such as campesterol and brassicasterol, do not inhibit the action of sitosterol and probably act as effective as the latter. Thus, by the term sitosterol I include B-sitosterol and other naturally occurring products that may be extracted along from soya oil, Tall oil, and cottonseed oil and generally termed sitosterol.

To achieve the foregoing objects of this invention, my process in outline is essentially as follows:

A. Beginning with Crude or Refined Wool Grease l. Saponification of the wool grease to produce essentially a mixture of wool wax alcohols and metallic salts (soaps) of wool wax fatty acids.

2. Separation of the wool wax alcohols from the soaps.

3. Substantial removal of cholesterol from the wool wax alcohols without chemical damage to the residual wool wax alcohols.

4. Incorporating a mixture .of sterols, consisting mainly of naturally-occurring sitosterol into ,the spent wool wax alcohols.

5. Where desirable, subjecting the reconstituted and modified wool wax alcohols in whole or in part to further traditional refinement, such as moleculardistil-v lation, or other purification methods, to remove tarry, resinous-like materials; and to improve color and odor.

The result is a pale-yellowcrystalline-like solid mass, indistinguishable in appearance from refined natural" wool wax alcohols, possessing a pleasant odor, and exhibiting emulsifying properties equal to or superior to the natural" wool wax alcohols, depending upon the extent of purification."

B. Beginning With Commercially-Available Wool Wax Alcohols Another mode of preparation of my product consisted in extracting cholesterol from commerciallyavailable wool wax alcohols, and incorporating the new sterol into the residual alcohol mixture, and refining the mixture to'uniformity and to the desirable characteristics mentioned in the foregoing DETAILED DESCRIPTION The following examples illustrate the invention:

EXAMPLE I The essentially solvent-free mixture of soaps and wool grease alcohols resulting from the saponification of wool grease, is treated with a suitable solvent, which dissolves the wool grease alcohols and leaves the solid metallic salts of the fatty acids. The latter are separated from the solution by filtration, or centrifuging. The solvent is distilled from the solution of the wool wax alcohols, and the cholesterol is removed from the wool wax alcohols by conventional methods such as those described in Truters' Wool Wax (loc. cit.), pp. -194 (62 references on the Isolation of Cholesterol); J. Th. Hackmann, Rec. Trav. Chim. 69, 433 (1950); British Patent 622,725 (1949); H. W. Knol, U.S. Pat. No. 2,536,753 (1951).

The crude soya, tallol, or cottonseed sitosterolsmay be separated by methodssuch as are described by P. L. Julian in U.S. Pat. Nos. 2,218,97l (1940); 2,273,045 (I942) and 2,273,046 (1942); also by Overhoff and Hackmann, Canadian Patent. 519,754 (1955), and Greiner and Fevig, Ind. & Eng. Chem. 53, 949 (1961). The crude sitosterols may be refined by crystallization or by separating them from resins, etc., as described in' kg. modified wool wax alcohols, m.p. in the range of 89-90 C.

EXAMPLE 2 EXAMPLE 3 Still another 80 kg. of modified and greatly improved wool wax alcohols, were prepared as follows: A solution of wool wax alcohols, from which the cholesterol had been essentially removed, was concentrated, whereupon an average of 60 percent of the higher melting alcohols crystallized as an almost colorless product. The latter was separated from the supernatant liquors, which liquors on freeing from low-boiling solvent, were subjected to molecular distillation, yielding an almost colorless distillate of relatively lower boiling wool wax alcohols in essentially quantitative yield. This latter fraction was added to the crystals and to this mixture 25 kg. of highly-purified sitosterol was added. The mixture was cautiously melted (in an atmosphere of nitrogen) to a uniform consistency, antioxidant added, and allowed to cool to a pale yellow solid. This mixture of modified wool wax alcohols represented for some cosmetic purposes a great improvement over those described in Examples 1 and 2. Moreover, this preparation obviates the necessity of subjecting the whole alcohol mixture (including the sitosterol) to the expensive molecular distillation, thus improving the economics of the preparation.

EXAMPLE4 A 50 g. sample ofa solution prepared by dissolving 6 g. modified wool wax alcohols (from Example 1) in 48 g. Protol, USP (white mineral oil of Sonneborn Division, Witco Chemical Company, having a specific gravity at 60 F. of 0.970-0.880, Saybolt viscosity at 100 F. 180-190, and Kinematic viscosity at 37.8 F. 38.6-40.9) was heated to ca. 60 C. To this solution was added water, heated to ca. 60 C., in approximately 10 ml. quantities at a time, while the mixture was beaten in a Sunbeam Mixmaster, Model MMZOOWS, at speed 4. Water was added at a rate so that the previous quantity was absorbed before the next quantity was added. After 100 ml. water had been added, absorption was more rapid and water could be added in larger portions (ca. 30-40 ml.). The average total water absorption was 793 ml. After many such runs with this preparation (from Example 1) and others as prepared in Examples 2 and 3, using soya sterols and sterols isolated from Tall oil, 1 rated the emulsion stabilities, resulting from the water absorption as follows:

Poor= Emulsion breaks in ca. 3 days.

Fair= Emulsion stands firm 1 to 2 weeks.

Good" Emulsion stands firm 1 month.

Excellent" Emulsion stands firm several months. The emulsion in Example 4 is rated good."

The sterols were isolated from Tall Oil as indicated in U.S. pat. Nos. 2,218,971, 2,273,045 and 2,273,046 and/or U.S. Pat. No. 2,536,753.

EXAMPLE 5 A 50 g. sample of solution as prepared in Example 4, except originating from modified wool wax alcohols as described in Example 2, was treated as in Example 4. The average total water absorption was 1,153 ml. to form an emulsion of excellent stability.

EXAMPLE 6 A 50 g. sample of solution as prepared in Example 4, except containing only wool wax alcohols commercially available from Takasago Perfumery Company, Ltd., Japan, m.p. 52 C., was treated as in Example 4. The average total water absorption was 676 ml. to give an emulsion of poor stability.

EXAMPLE 7 A 50 g. sample of solution as prepared in Example 4, except containing only wool wax alcohols commercially available from Takasago Perfumery Co., Ltd. (but which alcohols 1 had subjected to molecular distillation at 200/25-35 microns in percent yield), m.p. 61 C., was treated as in Example 4. The average total water absorption was 865 ml. to form an emulsion of fair stability.

EXAMPLE 8 A 50 g. sample of solution was prepared in Example 4, except containing only wool wax alcohols commercially available from Croda, Inc., New York, under the label Hartolan, m.p. 65 C., was treated as in Example 4. The average total water absorption was 993 ml. to give an emulsion of good stability.-

EXAMPLE 9 A 50 g. sample of solution as prepared in Example 4, except containing only wool wax alcohols commercially available from Croda, Inc., under the label Super Hartolan, m.p. 75 C., was treated as in Example 4. The average total water absorption was 1,187 ml. to form an emulsion of excellent stability.

EXAMPLE 10 A 50 g. sample of solution as prepared in Example 4, except containing only wool wax alcohols commercially available from Westbrook-Marriner, lnc., Lawrence, Mass. under the label Argowax, Standard, m.p. 64 C., was treated as in Example 4. The average water absorption was 858 ml. to give an emulsion of good stability.

EXAMPLE 1 1 A 50 g. sample ofsolution as prepared in Example 4, except containing only wool wax alcohols commercially available from Westbrook-Marriner, lnc., under the label Argowax, Distilled, m.p. 73 C., was treated as in Example 4. The average total water absorption was 1,028 ml. to form an emulsion of excellent stability.

EXAMPLE 12 A 5 g. sample of modified wool wax alcohols (Example 1) was dissolved in 45 g. Carnation, F.F. mineral oil (white mineral oil of Sonneborn Division, Witco Chemical Company, specific gravity at 60 F. 0.835-0.845, Saybolt viscosity at F. 65-75, Kinematic viscosity at 37.8 F. l l.7l4.4). This solution Average was heated to ca. 60 C. and water at 60 C. was added Pg lgf as in Example 1. The water absorption was l,l8l ml. to M tltllpo Avvlagg a t m il (laxliltltll '.1., -.t'0l itcl ly '0 '2 give an emulsion of excellent stability. Alcohols l z vuhw i, mm 5 Modified and im- EXAMPLE 13 proved wool wax alcohols (Ex- A 5 g. sample of modified wool wax alcohols ample 1) 90 at 1.1 131 1.

Modified and i111- prepared as in Example 2, was treated as in Example proved W001 WM 12. The average total water absorption was l,605 ml. to I O g gfg gfl fl 7o 32 l 145 4. Takasa otlloholsn e2 32 1.4 150 give an emulsion of excellent stability. ra u 58 28 Max. 2.0 Max *5 Super hartolan 60 30 Max. *1. 5 120-160 Max. *5 EXAMPLE l4 Argowax standard 04 M 1. 8 1169 J. O Argowux distilled... 73 4t. 5 1. 2 162 5.0

A 5 g. sample of modified wool wax alcohols prepared as in Example 3, and treated as in Example 12, absorbed an average total of 1,780 ml. of water to give an emulsion of excellent stability. This is especially significant in that this preparation is the most commercially favored one and also displays other desirable characteristics, such as improved color and lowered melting point.

Based upon current economics, l find it desirable to remove substantially all of the removable cholesterol from the wool wax alcohols and replace the same with economically feasible to replace about l5 percentto about 35 percent of the weight of the alcohol fraction of wool grease the replacement by sitosterol being EXAMPLE 15 desirably approximately quantitative as far as, the

equivalent weights of the two sterols are concerned. A 5 8- sample of wool wax commercially Advantageously, an antioxidant is added in the range available from Takasago Perfumery w was of about 0.01 percent to about 1 percent normally E as in Example The average total water about 0.1, percent of the weight of the mixture of the Q P was 1,008 to g an emulsion of g wax alcohols in which the cholesterol has been substany' tially replaced by sitosterol. in some instances, however, this may not be necessary. At present, butylated EXAMPLE 16 hydroxytoluene, is commonly employed for this pur- A 5 g. sample of wool wax alcohols commercially pose althoughawide variety of antioxidantsfor organic available from Takasago Perfumery Co., Ltd. (but materials is currently available to those skilled in the which we had subjected to molecular distillation at art- For mp the t h Pharmacopoeia 200/25-B35 microns in 80 er i ld) was t d as specifies that a wool wax alcohol mixture contains not in Example 12. The average total water absorption was less than 500 more than L Parts million of 1,433 ml. to give an emulsion of good stability. lated hydl'oxyanisole of butylated hydroxytoluene- While the foregoing examples illustrate this inven- EXAMPLE 17 tion, lam notlimited by them. Thus, for example, the

0 quantity of sltosterol incorporated into the spent A 5 g. sample of wool wax alcohols commercially alcohols (the latter referring to alcohols freed from available under the label Hartolan was treated as in Exmost and/or essentially all of the cholesterol) might ample 12. The average total water absorption was vary, depending upon the desired melting point of the 1,608 ml. to form an emulsion of excellent stability. final product, the mineral oil carrier, and the particular emulsifying use to which the newly-constituted alcohols might be put. EXAMPLE it will be appreciated that the invention provides a A 5 g. sample of wool wax alcohols commercially product which even though substantially cholesterol available under the label Super Hartolan was treated as free still has at least about 30 percent digitonin in Example 12. The average total water absorption was 0 precipitable steroids. This new compositionof matter 1,630 ml. to give an emulsion of excellent stability. removes at least in large part the hazard of possible cholesterol absorption into the blood stream, particu- EXAMPLE 19 larly when such a material may be frequently applied to the skin.

5 8- Sample of wool wax aleohols commercially The invention also provides a process for Y the available under the label Argowax Sandal'd was economic production of cholesterol, in these days of treated as in Example l2. The average total water abd li i l grease production, d constantly i sorption was 1,3 to afford an emulsion Of excelcreasing demand for cholesterol for vitamin lent Y- production, by extracting cholesterol from commercially-available wool wax alcohols and returning the EXAMPLE 20 essentially cholesterol-free residues to their former value as emulsifiers by producing a sitosterol-fortified A 5 8- Sample of wool wax alcohols commercially product thus doubling the revenue because of utilizaavailable under label g Distmed was treated as tion of an essentially cholesterol-free residue hitherto in Example 12. The average total ater absorption a considered useless. The resultant product is enhanced 1,803 ml. to afford an emulsion f exc llent stability. by molecular distillation to give a color refinement and A comparison of pertinent characteristics is as folfreedom from resinous or polymeric and/or high-boillows: ing materials.

sitosterol. Thus, under currentconditions, it is.

Advantageously in this operation the refined composition may represent as high as 60-70 percent of the material subjected to distillation. Since the molecular distillation is an expensive process, particularly for high-boiling and heat sensitive products, this guarantees an economic advantage over present commercially distilled wool wax alcohols.

lclaim:

1. A new and useful cosmetic emollient water-absorbing mineral oil-emulsifying pale yellow crystallinelike solid mass composition of matter comprising spent wool wax alcohols which are poor emulsifiers when essentially freed of the cholesterol constituent which imparts emulsion forming ability thereto, and a sufficient quantity of a sterol consisting principally of sitosterol as to bring these spent wool wax alcohols up to the emulsifying capacity of the intact cholesterol-bearing wool wax alcohols.

2. A new composition of matter in accordance with claim 1 comprising wool wax alcohols from which cholesterol has been substantially removed and replaced entirely by sitosterol in sufficient quantities to represent substantially the emulsification equivalent of replaced cholesterol.

3. A new composition according to claim 2 in which the sitosterol represents from about 15 percent to about 35 percent of the weight of the wool wax alcohols.

4. A new composition according to claim 2 in combination with a mineral oil carrier, said composition being characterized therein to absorb up to several hundred times its weight of water, forming stable emulsion, principally of the water-in-oil type, and useful in the production of a wide variety of cosmetic creams and lotions.

5. A new composition according to claim 2 in which about 0.01 percent to about 1 percent of an antioxidant has been added.

6. A new composition according to claim 5 in which said antioxidant constitutes about 0.l percent of the weight of the modified wax alcohols.

7. A composition of matter according to claim 2 in which the sitosterol is soya sitosterol.

8. A composition of matter according to claim 2 in which the sitosterol is a Tall Oil derivative. 

2. A new composition of matter in accordance with claim 1 comprising wool wax alcohols from which cholesterol has been substantially removed and replaced entirely by sitosterol in sufficient quantities to represent substantially the emulsification equivalent of replaced cholesterol.
 3. A new composition according to claim 2 in which the sitosterol represents from about 15 percent to about 35 percent of the weight of the wool wax alcohols.
 4. A new composition according to claim 2 in combination with a mineral oil carrier, said composition being chAracterized therein to absorb up to several hundred times its weight of water, forming stable emulsion, principally of the water-in-oil type, and useful in the production of a wide variety of cosmetic creams and lotions.
 5. A new composition according to claim 2 in which about 0.01 percent to about 1 percent of an antioxidant has been added.
 6. A new composition according to claim 5 in which said antioxidant constitutes about 0.1 percent of the weight of the modified wax alcohols.
 7. A composition of matter according to claim 2 in which the sitosterol is soya sitosterol.
 8. A composition of matter according to claim 2 in which the sitosterol is a Tall Oil derivative. 